No presente estudo objetivou-se avaliar o desempenho do etanol e isopropanol, absoluto e azeotrópico, na extração de óleo de macadâmia e milho. Nesse sentido, foram realizados experimentos de extração em batelada para determinar os efeitos do tipo de solvente e temperatura sobre o índice de retenção, rendimento de extração, qualidade do óleo e fração proteica. Assim, torta parcialmente desengordurada de macadâmia sem pré-tratamento prévio à etapa de extração (teor de lipídios 57,4 ± 0,7 % em base seca) foi submetida a extração, nas temperaturas de 60, 75 e 90 °C, enquanto as extrações de óleo do gérmen de milho em pellets (teor de lipídios 12,61 ± 0,05 % em base seca) foram realizadas a 50, 60, 70 e 80 °C. Os experimentos de extração em correntes cruzadas foram realizados a 70 e 75 °C para o gérmen de milho e a macadâmia, respectivamente. Os resultados mostraram que o rendimento de extração de óleo de macadâmia e milho é influenciado pelo tipo solvente, temperatura e pré-tratamento do material, sendo que com isopropanol absoluto, a 90 °C, foi possível extrair 66 % do óleo de macadâmia e a 80 °C, 87 % do óleo de milho. O índice de retenção de solução aderida as fibras (IR) foi impactado pelo tipo de solvente e características da matéria-prima, obtendo-se valores de IR maiores nas fases rafinado de macadâmia. A composição em ácidos graxos dos óleos de gérmen de milho extraídos com os solventes alcoólicos foi típica do óleo de milho, com predominância dos ácidos graxos oleico (34 %) e linoleico (48 %). As fases rafinado dos dois materiais apresentaram teor de proteínas maior que as matérias-primas iniciais, no entanto as condições do processo de extração impactaram negativamente no índice de solubilidade de nitrogênio, tornando inviável a produção de concentrado proteico de gérmen de milho. Para o óleo de milho a extração de tocoferóis e tocotrienóis foi maior com etanol, enquanto que com isopropanol conseguiu-se uma maior extração de carotenoides, o que pode ser decorrente da polaridade destes compostos bioativos. Os óleos de macadâmia extraídos com os solventes alcoólicos apresentaram maior estabilidade oxidativa (mais de 37 horas) quando comparados ao óleo bruto obtido por prensagem industrial (11,7 horas), sendo possível inferir que o uso dos solventes alcoólicos possibilita a extração de compostos que contribuem para o aumento da estabilidade do óleo. Nos experimentos em correntes cruzadas foi observado que para desengordurar a macadâmia com etanol e isopropanol absoluto são necessários mais de quatro estágios de contato, enquanto para o gérmen de milho dois estágios são suficientes. Em relação aos concentrados proteicos de macadâmia, o rendimento foi maior com os rafinados oriundos das extrações com isopropanol absoluto (13 %). Estes concentrados apresentaram boa capacidade de retenção de água e óleo (aproximadamente 2 g/g de concentrado) e estabilidade e atividade de emulsão na faixa de 56 a 59 %, desta forma pode-se sugerir que estes produtos apresentam potencial para seu aproveitamento na indústria de alimentos. A partir dos resultados pode-se inferir que a utilização dos solventes alcoólicos na extração de óleo de milho e macadâmia é tecnicamente viável, no entanto o desempenho dos solventes alcoólicos é influenciado pelas características da matéria-prima e pelo pré-tratamento do material sólido prévio à etapa de extração, obtendo-se maiores rendimentos de extração de óleo com o gérmen de milho em pellets. Também é possível inferir que os solventes em grau absoluto impactam menos na solubilidade das proteínas, permitindo a produção de concentrados proteicos de macadâmia com propriedades funcionais adequadas para seu uso na indústria de alimentos. / The objective of this study was to evaluate the performance of ethanol and isopropanol, absolute and azeotropic, in the extraction of macadamia and corn oil. Accordingly, extraction experiments were performed in batch to determine the effect of solvent type and temperature on retention index, extraction yield, quality indices of oil and protein fraction. Thus, partially defatted macadamia meal without pre-treatment prior to the extraction step (lipid content 57.4 ± 0.7 % on dry basis) was submitted to extraction at temperatures of 60, 75 and 90 °C, while oil extractions of corn germ in pellets (lipid content 12.61 ± 0.05 % on dry basis) were performed at 50, 60, 70 and 80 °C. The crosscurrent extraction experiments were performed at 70 and 75 °C for corn germ and macadamia, respectively. The results showed that the oil extraction yield of macadamia and corn is influenced by the solvent type, temperature and pre-treatment of the material, being that with absolute isopropanol at 90 °C, it was possible to extract 66 % of the macadamia oil and 87 % of the corn oil at 80 °C. The retention index of the solution adhered to the fibers (RI) was affected by the type of solvent and characteristics of the raw material, obtaining higher values of RI in the raffinate phases of macadamia. The fatty acid composition of corn germ oils extracted with alcoholic solvents was typical of corn oil, with predominance of oleic acid (34 %) and linoleic acid (48 %). The raffinate phases of the two materials showed higher protein content than the initial raw materials, however the conditions of the oil extraction process had a negative impact on the nitrogen solubility index, turning the production of protein concentrate from corn germ infeasible. For corn oil the extraction of tocopherols and tocotrienols was higher with ethanol, whereas with isopropanol a greater extraction of carotenoids was obtained, which can be due to the polarity of these bioactive compounds. Macadamia oils extracted with the alcoholic solvents showed higher oxidative stability (more than 37 hours) when compared to crude oil obtained by industrial cold pressing (11.7 hours). It is possible to infer that the use of alcoholic solvents enables to extract compounds that contribute to the increase of oil stability. In the crosscurrent extraction experiments it was observed that to produce defatted macadamia with absolute ethanol and isopropanol more than four stages of contact are required, whereas for the corn germ two stages are sufficient. Regarding protein concentrates of macadamia, the yield was higher with raffinate phases coming from the extractions with absolute isopropanol (13 %). These concentrates showed good water and oil retention capacity (approximately 2 g/g of concentrate) and emulsion stability and activity in the range of 56 to 59 %, therefore it can be suggested that these products have potential for their use in the food industry. From the results it can be inferred that the use of the alcoholic solvents in the extraction of corn and macadamia oil is technically feasible, however the performance of the alcoholic solvents is influenced by the characteristics of the raw material and by pre-treatment of the solid material prior to the extraction step, obtaining the highest oil extraction yields with the corn germ in pellets. Also, it is possible to infer that the solvents in absolute degree impact less on the solubility of the proteins, enabling the production of macadamia protein concentrates with functional properties suitable for use in the food industry.

A macadâmia (Macadamia integrifolia) é considerada comercialmente uma das nozes mais importantes do mundo por seus atributos sensoriais e nutricionais. Dentre as etapas do beneficiamento desta noz, destacam-se a secagem e a torra como processos térmicos diretamente ligados a sua qualidade. Contudo, eles têm sido relacionados à diminuição da estabilidade oxidativa e da capacidade antioxidante de compostos bioativos, como os ácidos fenólicos. Sendo assim, o objetivo deste trabalho foi caracterizar e comparar a noz macadâmia submetida às etapas de secagem (crua) e de torra, quanto a composição química e sua atividade antioxidante in vitro. Os ensaios realizados para a composição centesimal demonstraram que não houve diferença (p<0,05) entre as amostras crua e torrada, exceto pela umidade e cinzas. Observou-se que macadâmia, cura ou torrada, é uma grande fonte de lipídeos (~77g/100g amostra). Não se verificou diferença no perfil dos ácidos graxos entre as amostras analisadas, prevalecendo monoinsaturados (~58g/100g amostra). Para a avaliação da atividade antioxidante, foram obtidos, das amostras cruas e torradas, os extratos etéreo (EE), alcoólico (EAlc) e aquoso (EAq) e as frações de ácidos fenólicos livre (AFL), esterificados solúveis (AFS) e insolúveis-ligados (AFI). Quanto ao teor de fenólicos totais, através do método com o reagente de Folin-Ciocalteau, o extrato que se destacou foi o EAq, tanto para macadâmia crua quanto para torrada, com os maiores valores em relação aos outros extratos, mas ainda foram menores que as frações. A macadâmia torrada obteve os maiores teores de fenólicos totais com AFL e AFS. A atividade antioxidante foi testada através dos métodos de redução do radical DPPH, de co-oxidação do sistema &#946;-caroteno/ácido linoleico e de oxidação lipídica acelerada em Rancimat. No teste de redução do DPPH, a macadâmia crua foi mais eficiente que a torrada apenas no EE e na AFI. Já para o EAq, o EAlc, a AFL e a AFS, a macadâmia torrada apresentou as melhores porcentagens de redução. No sistema &#946;-caroteno/ácido linoleico, os EAqs tiveram maiores porcentagens de inibição da oxidação que os demais extratos; todas as frações apresentaram porcentagens de inibição muito superiores às dos extratos, mesmo em concentrações menores. Notou-se também que houve queda na capacidade de inibição da oxidação do EE e das três frações (AFL, AFS e AFI), quando se comparam a amostra crua em relação à torrada. No ensaio em Rancimat, o EAlc foi o único, entre extratos e frações de ambas as amostras, a diferir significativamente do controle-negativo em sua ação protetora, entretanto não foi mais eficiente que o TBHQ, utilizado como controle-positivo. Neste estudo, a diferença de atividade entre os métodos ficou clara, contudo também se evidenciou que o tratamento térmico da torra é capaz de alterar a capacidade antioxidante dos compostos fenólicos presentes na macadâmia. / Macadamia (Macadamia integrifolia) is considered one of the most important nuts in the world for their nutritional and sensory attributes. In the macadâmia nut processing, drying and roasting steps stand out because they are thermal processes directly related with its quality. However, they have been associated to the decrease of oxidative stability and antioxidant activity of bioactive compounds such as phenolic acids. Therefore, the aim of this study was to characterize and compare the dried (raw) and roasted macadamia nuts, their chemical composition and in vitro antioxidant activity. The composition assays shown that there was no difference between raw and roasted samples of macadamia (p<0,05), except for moisture and ash. It was also observed that both samples are source of oil (~77g/100g macadamia). There was no difference (p<0,05) in the fatty acids profile of the samples, with the predominance of monounsaturated fatty acids (~58g/100g macadamia). For the evaluation of antioxidant activity, the ether (EE), alcoholic (EAlc) and aqueous (EAq) extracts and the free phenolic acids (AFL), soluble esterified acids (AFS) and insoluble-bound acids (AFI) fractions were obtained from raw and roasted samples. In the total phenolic content, by Folin-Ciocalteau method, the EAq stood out for raw and roasted macadamia nuts with a high content, compared with the other extracts, but it was lower than the acid phenolic fractions. The roasted macadamias showed the highest levels of total phenolics in AFL and AFS. The antioxidant activity was obtained by the methods of DPPH radical reduction, of &#946;-carotene/linoleic acid co-oxidation system and accelerated lipid oxidation in Rancimat. In the DPPH test, raw macadamia reduced more efficiently than roasted only in EE and AFI. For the EAq, EAlc, AFL and AFS, the roasted macadamia nuts showed the best percentages of reduction. In &#946;-carotene/linoleic acid system, EAqs of both samples showed similar results and had the highest percentage of oxidation inhibition than the other extracts. All of fractions showed much higher percentages of inhibition than extracts, even at lower concentrations. A decrease in the ability to inhibit oxidation of EE and the three fractions (AFL, AFS and AFI) was also noticed, when comparing the raw samples with the roasted. In Rancimat test, the EAlc was the only, of the extracts and fractions of both samples, witch differed significantly from negative control in its protective activity; however it was not more effective than TBHQ, used as positive control. In this study, the differences between the methods were noticeable, but it was also showed that the thermal treatment of the roasting was able to modify the antioxidant capacity of phenolic compounds in macadamia nuts.

Orientador: Gustavo Henrique de Almeida Teixeira / Coorientador: Marcos David Ferreira / Banca: Luciana Manoel de Oliveira / Banca: José Dalton Cruz Pessoa / Banca: Luis Vitor Silva do Sacramento / Banca: Luis Carlos Cunha Júnior / Resumo: Objetivo: Desenvolver métodos analíticos com uso da espectroscopia do infravermelho próximo (NIRS) e ressonância magnética nuclear (NMR) para a melhoria do processo de controle de qualidade de nozes macadâmia (Macadamia integrifolia Maiden & Betche). Métodos: Foram coletadas nozes de macadâmia intactas de várias cultivares (HAES 246, 'IAC 4-20', 'IAC 2-23', 'IAC 5-10','IAC 8-17',HAES 344, HAES 660, IAC 4-12 B e IAC Campinas B) e amêndoas sem defeitos e que apresentavam diferentes defeitos, ou seja, amêndoas imaturas; amêndoas danos causados por picada de insetos, amêndoas mofadas e amêndoas descoloridas. Além disso, foi analisado o efeito de diferentes temperaturas de secagem quanto os paramentos de oxidação, índice de peróxido (IP) e de acidez (IA). Os espectros NIR foram coletados na superfície das nozes intactas e também das amêndoas (NIRS e NMR-TD) e estes foram utilizados para a construção dos modelos de classificação e predição utilizando análise discriminante linear por componente principal (PCA-LDA), algoritmo genético com análise discriminante linear (GA-LDA) e regressão por mínimos quadrados parciais (PLSR). Resultados: Em relação a classificação das cultivares, os modelos desenvolvidos com GA-LDA resultaram em acurácia de 71,57% com os espectros pré-processados com suavização de Savitzky-Golay. Não foi observado efeito do processo de secagem no IP e IA. Os melhores resultados de predição do IP (R²c=0,57 e SEP=0,55 meq·kg−1) e IA (SEP=0.14%, R2C=0.29) foram obtidos ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Objective: To develop analytical methods with the use of near infrared spectroscopy (NIRS) and nuclear magnetic resonance (NMR) to improve the quality control process of macadamia nuts (Macadamia integrifolia Maiden & Betche). Methods: Intact macadamia nuts were collected from several cultivars (HAES 246, 'IAC 4-20', 'IAC 2-23', 'IAC 5-10','IAC 8-17',HAES 344, HAES 660, IAC 4-12 B, and IAC Campinas B) and kernels that had different defects, as such: nuts without defects; immature kernels; damages caused by insect, mold kernels, and discolored kernels. In addition, the effect of different types of drying on the oxidation parameters, peroxide value (PV) and acidity index (AI) were analyzed. The NIR spectra were collected on the surface of intact nuts and kernels (NIR and NMR-TD), and the spetra were used to develop the classification and prediction models using linear discriminant analysis by principal component analysis (PCA-LDA), genetic algorithm with linear discriminant analysis (GA-LDA), and partial least squares regression (PLSR). Results: In relation to cultivar classification, the models developed with GA-LDA resulted in an accuracy of 71,57% with Savitzky-Golay smoothing pre-processed spectra. No effect of the drying process was observed on IP and AI. The best PV prediction results (R²c = 0.57 and SEP = 0.55 meq.kg-1 ) and AI (SEP = 0.14 %, R2 C = 0.29) were obtained employing PLSR. Regarding kernel defects, it was possible to obtain an accuracy and specificity of 97.8% and 100% using GA-LDA, respectively. The best NMR classification models using PCA-LDA, achieving 85.7 % accuracy for the training set... (Complete abstract click electronic access below) / Doutor

Typescript. Thesis (Ph. D.)--University of Hawaii, 1951. Bibliography: leaves [98]-103.

Submitted by SIDNÉIA TEREZINHA SOARES DE MATOS null (sidimatos@yahoo.com.br) on 2017-04-12T16:44:54Z No. of bitstreams: 1 Dissetação.pdf: 1367407 bytes, checksum: 11ea0905bcfc7e04d2170a949665fe94 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-04-17T20:44:05Z (GMT) No. of bitstreams: 1 matos_sts_me_jabo.pdf: 1367407 bytes, checksum: 11ea0905bcfc7e04d2170a949665fe94 (MD5) / Made available in DSpace on 2017-04-17T20:44:05Z (GMT). No. of bitstreams: 1 matos_sts_me_jabo.pdf: 1367407 bytes, checksum: 11ea0905bcfc7e04d2170a949665fe94 (MD5) Previous issue date: 2017-02-17 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A nogueira-macadâmia (Macadamia integrifolia Maiden e Betche), originária da Austrália, encontra-se em expansão no Brasil. Por ser uma cultura recentemente introduzida no País, a maioria das informações e as tecnologias recomendadas para sua produção foram adaptadas de pesquisas efetuadas para as condições edafoclimáticas dos Estados Unidos e da Austrália. Esse fato ressalta a necessidade de se desenvolver estudos sobre a fauna entomológica, visando ao manejo integrado de pragas dessa nogueira. No presente estudo, foi realizado levantamento populacional de insetos em nogueira-macadâmia em Jaboticabal, São Paulo. O objetivo foi identificar as principais espécies de insetos fitófagos e predadores e determinar as espécies predominantes por meio de estudos de flutuação populacional desses organismos em relação aos estádios fenológicos da cultura. O total de 540 exemplares de insetos predadores foram coletados pertencentes a 8 ordens, 13 famílias e 37 espécies; os insetos fitófagos totalizaram 7588 exemplares de 5 ordens, 35 famílias e 83 espécies. Os predadores Chrysoperla externa (Hagen) (Neuropetra: Chrysopidae), Harmonia axyridis (Pallas) (Coleoptera: Coccinellidae), Allograpta hastata Fluke (Diptera: Syrphidae) e Nusalala sp. (Neuroptera: Hemerobiidae) e os fitófagos Toxoptera aurantii (Fonscolombe) Hemiptera: Aphididae), Frankliniella gardeniae Moulton (Tysanoptera: Thripidae), Haplothrips gowdeyi (Franklin) (Tysanoptera: Phlaeothripidae), Mormidea sp., Piezodorus sp. (Hemiptera: Pentatomidae), Zicca sp. (Hemiptera: Coreidae), Stenocoris sp. (Hemiptera: Alydidae), Diabrotica speciosa (Germar) (Coleoptera: Chrysomelidae), Charidotis marginella (Fabricius) (Coleoptera: Chrysomelidae), Ophiderma sp. (Hemiptera: Membracidae), Epitragus sp.3 (Coleoptera Tenebrionidae) e Ptilodactyla sp.2 (Coleoptera: Ptilodactylidae) classificaram-se como predominantes. Os maiores índices de diversidade e picos populacionais das espécies predominantes ocorreram no estádio de floração. / The macadamia nut (Macadamia integrifolia Maiden e Betche) is native from Australia and is in expansion in Brazil. It was recently introduced in the country, therefore, most of the knowledges and technologies recommended for production were adapted from researches conducted for soil and climatic conditions in United States and Australia. This fact highlights the importance of studies about the entomological fauna, aiming at the integrated pest management of this walnut. In this study was conducted a population survey of insects in macadamia nut in Jaboticabal, São Paulo. The objective was to identify the main species of phytophagous insects and predators and to determine the predominant species through the study of its population dynamics in relation to the phenological stages of the crop. A total of 540 predatory insects specimens belonging to eigth orders, 13 families and summing up 37 species were collected. A total of 7588 specimens of phytophagous insects from five orders, 35 families and and summing up 83 species were captured. The insect predators Chrysoperla externa (Hagen) (Neuropetra: Chrysopidae), Harmonia axyridis (Pallas) (Coleoptera: Coccinellidae), Allograpta hastata Fluke (Diptera: Syrphidae) e Nusalala sp. (Neuroptera: Hemerobiidae) and the insect phytophagous Toxoptera aurantii (Fonscolombe) Hemiptera: Aphididae), Frankliniella gardeniae Moulton (Tysanoptera: Thripidae), Haplothrips gowdeyi (Franklin) (Tysanoptera: Phlaeothripidae), Mormidea sp., Piezodorus sp. (Hemiptera: Pentatomidae), Zicca sp. (Hemiptera: Coreidae), Stenocoris sp. (Hemiptera: Alydidae), Diabrotica speciosa (Germar) (Coleoptera: Chrysomelidae), Charidotis marginella (Fabricius) (Coleoptera: Chrysomelidae), Ophiderma sp. (Hemiptera: Membracidae), Epitragus sp.3 (Coleoptera Tenebrionidae) e Ptilodactyla sp.2 (Coleoptera: Ptilodactylidae) were classified as predominant. The highest species diversity and population peak of predominant species occurred during the flowering stage.

A macadâmia (Macadamia integrifolia) é considerada comercialmente uma das nozes mais importantes do mundo por seus atributos sensoriais e nutricionais. Dentre as etapas do beneficiamento desta noz, destacam-se a secagem e a torra como processos térmicos diretamente ligados a sua qualidade. Contudo, eles têm sido relacionados à diminuição da estabilidade oxidativa e da capacidade antioxidante de compostos bioativos, como os ácidos fenólicos. Sendo assim, o objetivo deste trabalho foi caracterizar e comparar a noz macadâmia submetida às etapas de secagem (crua) e de torra, quanto a composição química e sua atividade antioxidante in vitro. Os ensaios realizados para a composição centesimal demonstraram que não houve diferença (p<0,05) entre as amostras crua e torrada, exceto pela umidade e cinzas. Observou-se que macadâmia, cura ou torrada, é uma grande fonte de lipídeos (~77g/100g amostra). Não se verificou diferença no perfil dos ácidos graxos entre as amostras analisadas, prevalecendo monoinsaturados (~58g/100g amostra). Para a avaliação da atividade antioxidante, foram obtidos, das amostras cruas e torradas, os extratos etéreo (EE), alcoólico (EAlc) e aquoso (EAq) e as frações de ácidos fenólicos livre (AFL), esterificados solúveis (AFS) e insolúveis-ligados (AFI). Quanto ao teor de fenólicos totais, através do método com o reagente de Folin-Ciocalteau, o extrato que se destacou foi o EAq, tanto para macadâmia crua quanto para torrada, com os maiores valores em relação aos outros extratos, mas ainda foram menores que as frações. A macadâmia torrada obteve os maiores teores de fenólicos totais com AFL e AFS. A atividade antioxidante foi testada através dos métodos de redução do radical DPPH, de co-oxidação do sistema &#946;-caroteno/ácido linoleico e de oxidação lipídica acelerada em Rancimat. No teste de redução do DPPH, a macadâmia crua foi mais eficiente que a torrada apenas no EE e na AFI. Já para o EAq, o EAlc, a AFL e a AFS, a macadâmia torrada apresentou as melhores porcentagens de redução. No sistema &#946;-caroteno/ácido linoleico, os EAqs tiveram maiores porcentagens de inibição da oxidação que os demais extratos; todas as frações apresentaram porcentagens de inibição muito superiores às dos extratos, mesmo em concentrações menores. Notou-se também que houve queda na capacidade de inibição da oxidação do EE e das três frações (AFL, AFS e AFI), quando se comparam a amostra crua em relação à torrada. No ensaio em Rancimat, o EAlc foi o único, entre extratos e frações de ambas as amostras, a diferir significativamente do controle-negativo em sua ação protetora, entretanto não foi mais eficiente que o TBHQ, utilizado como controle-positivo. Neste estudo, a diferença de atividade entre os métodos ficou clara, contudo também se evidenciou que o tratamento térmico da torra é capaz de alterar a capacidade antioxidante dos compostos fenólicos presentes na macadâmia. / Macadamia (Macadamia integrifolia) is considered one of the most important nuts in the world for their nutritional and sensory attributes. In the macadâmia nut processing, drying and roasting steps stand out because they are thermal processes directly related with its quality. However, they have been associated to the decrease of oxidative stability and antioxidant activity of bioactive compounds such as phenolic acids. Therefore, the aim of this study was to characterize and compare the dried (raw) and roasted macadamia nuts, their chemical composition and in vitro antioxidant activity. The composition assays shown that there was no difference between raw and roasted samples of macadamia (p<0,05), except for moisture and ash. It was also observed that both samples are source of oil (~77g/100g macadamia). There was no difference (p<0,05) in the fatty acids profile of the samples, with the predominance of monounsaturated fatty acids (~58g/100g macadamia). For the evaluation of antioxidant activity, the ether (EE), alcoholic (EAlc) and aqueous (EAq) extracts and the free phenolic acids (AFL), soluble esterified acids (AFS) and insoluble-bound acids (AFI) fractions were obtained from raw and roasted samples. In the total phenolic content, by Folin-Ciocalteau method, the EAq stood out for raw and roasted macadamia nuts with a high content, compared with the other extracts, but it was lower than the acid phenolic fractions. The roasted macadamias showed the highest levels of total phenolics in AFL and AFS. The antioxidant activity was obtained by the methods of DPPH radical reduction, of &#946;-carotene/linoleic acid co-oxidation system and accelerated lipid oxidation in Rancimat. In the DPPH test, raw macadamia reduced more efficiently than roasted only in EE and AFI. For the EAq, EAlc, AFL and AFS, the roasted macadamia nuts showed the best percentages of reduction. In &#946;-carotene/linoleic acid system, EAqs of both samples showed similar results and had the highest percentage of oxidation inhibition than the other extracts. All of fractions showed much higher percentages of inhibition than extracts, even at lower concentrations. A decrease in the ability to inhibit oxidation of EE and the three fractions (AFL, AFS and AFI) was also noticed, when comparing the raw samples with the roasted. In Rancimat test, the EAlc was the only, of the extracts and fractions of both samples, witch differed significantly from negative control in its protective activity; however it was not more effective than TBHQ, used as positive control. In this study, the differences between the methods were noticeable, but it was also showed that the thermal treatment of the roasting was able to modify the antioxidant capacity of phenolic compounds in macadamia nuts.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Macadamia activated carbon (MAC) was impregnated with different concentrations of nitric acid and heated under reflux to improve the structural characteristics of the adsorbent for both considerable reduction and enhanced removal of Cr(VI). The chemical oxidation of ACs increased the surface oxygenated functional groups. Adsorption of Cr(VI) was carried out by varying parameters such as contact time, pH, concentration, and adsorbent dosage. The optimum operating conditions for the adsorption of Cr(VI) were pH 1, contact time 240 min, adsorbent dosage 10.67 g/L and Cr(VI) concentration 100 mg/L. The results showed that the Macadamia–based AC could be used efficiently for the treatment of chromium-containing solutions as a low-cost alternative compared to commercial AC and other adsorbent reported. The results showed that treated MAC performed better than untreated MAC, signifying the effect of secondary treatment on the enhanced removal of pollutants. Comparable to the application of ACs is the development of imprinting technologies for selective metal ion remediation in environmental samples. The combination of ion imprinting effects and functionalized carbon adsorbents produce materials which effectively remove and selectively recognize the target analyte. Macadamia activated carbon (MAC) was chemically pre-treated with nitric acid to generate carboxyl groups on the surface. The carboxylated MAC was then reacted with triethylenetetramine, N,N’-diisopropylcarbodiimide and CrCl3.6H2O to produce MACN20-imprinted sorbents (MACN20-IIP). MACN20-non imprinted (MACN20-NIP) counterparts were prepared, but Cr3+ was excluded in the synthesis. Alteration of surface structural characteristics and characterization of prepared adsorbents as confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, Brunauer–Emmett–Teller and scanning electron microscopy. MACN20-IIP and MACN20-NIP adsorbents were evaluated for their Cr3+ uptake from aqueous solution in batch format. Maximum conditions were achieved at pH 5, 50 mg/L Cr(III) initial concentration and 33.33 g/L of adsorbent dosage. Presence of co-ions slightly diminished the removal of Cr(III) by MAC-IIP adsorbents. Application of the MACN20-IIP and MACN20-NIP on spiked acid mine drainage artificial sample led to collapse in the removal efficiency of MACN20-NIP while MACN20-IIP still showed good removal efficiencies. These results demonstrated that surface imprinting led to better adsorption rates and capacity. The data was better described by the Freundlich multilayer adsorption and pseudo-second order kinetic rate model. The combination of both the carbon sorbent and the surface-mediated IIPs effectively improved total chromium remediation in aqueous systems.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Persisting challenges associated with remediation of heavy metals from aqueous media have stirred the need for enhancement of current technologies. Cellulosic agro waste materials (AWM) as well as ion-imprinted polymers (IIP) have received ardent attention from researchers. These materials are often employed in the following industries: water and wastewater treatment, medical, pharmaceutical and packaging. Applications in water and wastewater treatment have gained significant interest due to desirable features they possess. In the case of AWM, these features include a tuneable surface area and poor porosity, basic surface functional groups and chemical stability. Some desired features in IIP include adsorption sites compatible for the ion imprint obtained after leaching with suitable reagents, rigidity and reusability. The efficacy of employing AWM and IIP for the remediation of toxic chromium from aqueous solution was explored. The current study is made up of part A and B. In part A, Macadamia nutshell powder was treated using HNO3, NaOH, as well as Fenton’s reagent. The three materials underwent a new modification which involved reacting treated adsorbents with cetyltrimethylammonium chloride (CTAC), followed by immobilization of 1,5' diphenylcarbazide (DPC) ligand. The adsorbents were ultimately washed, dried and stored for Cr(VI) batch adsorption experiments. Part B involved a synthesis of IIP and their non-imprinted polymer counterpart (NIP) for Cr(VI) sequestration in aqueous solution. This was done by precipitation polymerization of functional monomers, crosslinker and DPC-Cr(VI) complex as a template. Non-imprinted polymers were fashioned in a manner like that of IIP but with the exclusion of Cr(VI) ion template. Characterizations of the adsorbents were done using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), X-ray fluorescence (XRF), and carbon, hydrogen, nitrogen and sulphur (CHNS) analyzer. Batch adsorption experiments were done and parameters such as solution pH, adsorbent dosage, initial Cr(VI) concentration and contact time were optimized. Working solutions were analyzed using ultraviolet-visible (UV-Vis) and atomic absorption (AA) spectroscopy. Adsorption parameters found to be optimum for DPC immobilized cellulosic adsorbents were pH 1.4, adsorbent mass of 0.1 g, 100 mg/L initial concentration and 125 minutes of contact time. The adsorption parameters determined to be optimum for IIP and NIP were pH 2.6, 0.2 g adsorbent mass, 80 mg/L initial concentration and 240 minutes of contact time. Reusability studies demonstrated the potential of adsorbents to remove Cr(VI) ions from aqueous media after successive adsorption-desorption cycles. Selectivity studies indicated that DPC immobilized adsorbents as well as IIP were able to selectively adsorb Cr(VI) ions from aqueous media in the presence of Zn(II), Cu(II), Co(II) and NI(II) ions. Kinetic models revealed that DPC immobilized cellulosic adsorbents and synthetic IIP were most fitting for pseudo-second order and pseudo first order, respectively. On the other hand, adsorption isotherm studies demonstrated that DPC immobilized cellulosic adsorbents and synthetic polymers were best fit for Freundlich and Langmuir adsorption isotherm, respectively.

Plasma gasification experiments were conducted on sucrose and crushed macadamia nutshells. The pilot-scale plasma gasification system used comprises a 15 kW DC plasma torch fitted to a 5 L gasification reactor. The DC plasma torch has an efficiency of ~30 % with most of the energy lost in the torch anode. For the macadamia nutshells, the plasma input-power was set at 9, 11 and 14 kW. At each power input setting, four different feed rates were investigated, namely 0.5, 0.7, 1.04 and 1.14 kg/h. It was observed that as the power increases, conversion increases from 48 % at 9 kW to higher than 80 % at 14 kW. It was also observed that higher mass feed rates increase the conversion. The lower heating values of the syngas produced during gasification increased with higher power inputs and higher feed rates. At a feed rate of 1 kg/h, the maximum calorific power value was 3.45 kW, at a torch setting of 14 kW. The highest power values obtained was slightly more than 4 kW. The effect of equivalence ratio (ER) was evaluated on the plasma gasification of sucrose. ER values of 1 and 2 were investigated. With an ER of 1, the CO/H2 ratio was 1.8 and the CO/CO2 ratio was 109. With an ER of 2, the CO/H2 ratio was 1.73, and the CO/CO2 ratio 18. As expected, an increase in ER enhances the formation of CO2. A low ER thus results in higher syngas quality. At equivalent conditions the homogenous, crystalline sucrose yielded a CO/CO2 ratio of 109, significantly higher than the 29 for plasma gasification of the macadamia nut shells. A contributing factor to having better quality syngas, was the smaller the average particle diameter of the sucrose, 0.4 mm, compared to the 10 mm of the crushed macadamia nut shells was. Another contributing factor could be that the available carbon in the macadamia nut shells structure are more strongly bonded than in sucrose. For additional insight, kinetic data for the pyrolysis of sucrose, fructose and glucose were obtained using a TGA-FTIR hyphenated system, at much lower heating rates than anticipated in plasma system, and TGA-DTG experiments on macadamia nut shells. Dynamic studies were performed on sucrose, fructose and glucose at heating rates of 5, 10, 15, 20 and 50 °C/min in an atmosphere of nitrogen flowing at 50 mL/min, and for the macadamia shell at heating rates of 5, 10 and 20 °C/min in an atmosphere of nitrogen flowing at 50 mL/min. The sugars yielded 80 % to 85 % conversion into gaseous products, while the conversion of the shells approached 90 %; the residue was biochar. The FTIR spectra showed the major products that form from the pyrolysis of sugars to be CO2, H2O, along with large quantities C-H-O-containing compounds, amongst them C5H4O2 and C6H6O3. The latter two compounds are probably condensible. / Dissertation (MEng)--University of Pretoria, 2020. / Chemical Engineering / MEng / Unrestricted

Saturated steam (SS) and propylene oxide (PPO) fumigation are two common methods to improve microbiological quality and safety of tree nuts. Validation of these processes is needed to ensure adequate control of bacterial pathogens. Since pathogens cannot be studied in food processing environments, surrogates with resistance comparable to the pathogens needed to be identified. The objective was to investigate the suitability of Enterococcus faecium, Pediococcus acidilactici, and Staphylococcus carnosus as surrogate bacteria for Salmonella spp. on whole cashews and macadamia nuts, processed with SS or PPO. Whole cashews and macadamia nuts were co-inoculated with a cocktail of Salmonella enterica and one of the three potential surrogates. Nuts were dried to original aw, packaged in poly-woven bags (2.3 kg) and commercially processed using vacuum assisted steam at 80 ͦ C or PPO fumigation. Salmonella and the potential surrogates were enumerated by serial dilution, and plated onto TSA with overlay of XLT-4 (Salmonella) or media selective for the potential surrogates. Mean log reductions (CFU/g) of Salmonella and each potential surrogate were compared using a paired T-test. SS results: reduction of Salmonella (6.0 ± 0.14) was significantly larger than E. faecium (4.3± 0.12), or P. acidilactici (3.7± 0.14) on whole cashews. Salmonella (5.9 ± 0.18) was significantly larger than P. acidilactici (4.4± 0.18) on whole macadamia nuts. PPO results: reduction of Salmonella (7.3 ± 0.19) was significantly greater than E. faecium (6.4± 0.31), or P. acidilactici (6.3± 0.33) on whole macadamia nuts. Reduction of Salmonella was significantly greater than E. faecium and P. acidilactici reduction on cashews. P. acidilactici may be considered a surrogate for Salmonella reduction on whole macadamia nuts and whole cashews processed using SS at 80 ͦ C. E. faecium and P. acidilactici may be considered surrogates for Salmonella reduction on whole macadamia nuts and whole cashews processed using PPO. Reduction of St. carnosus exceeded that of Salmonella indicating it is not a suitable surrogate for Salmonella using either processing intervention. / Master of Science in Life Sciences / Tree nuts are produced and consumed worldwide, playing a role as a snack or ingredient in foods in several cultures. Traditionally, tree nuts have been believed to be microbiologically safe due to their composition and lack of water available to harbor pathogenic bacterial growth. However, recent years have proven to be problematic for many tree nuts and nut products, numerous recalls have occurred in the United States for verified contamination of <i>Salmonella</i>. Since <i>Salmonella</i> can be found in food systems worldwide, and is a leading cause of foodborne illness due to bacterial contamination of food, steps must be taken to improve the safety of nuts grown locally and imported products. With several processing options for tree nuts, two that are commonly practiced to reduce microorganisms include a fumigation of product using propylene oxide (PPO) and a thermal inactivation treatment through use of saturated steam. The comparison of <i>Salmonella</i> inactivation and non-pathogenic surrogate bacteria on cashews and macadamia nuts, being processed in these two manners, was investigated. Possible bacteria strains that were investigated for surrogacy were <i>Enterococcus faecium</i> NRRL B2354 (ATCC #8459), <i>Pediococcus acidilactici</i> (ATCC #8042), and <i>Staphylococcus carnosus</i> (ATCC #51365). Surrogates are bacteria that have similar inactivation characteristics to <i>Salmonella</i> when processed, that can be purposely introduced before processing to ensure inactivation of <i>Salmonella</i> and is harmless if consumption occurs. Studies continue to ensure safety of tree nuts as well as complying with pending and future regulations.